JPH0449594B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel high-molecular-weight ultraviolet absorber and cosmetics containing the same, and more specifically, a novel high-molecular-weight ultraviolet absorber that is a copolymer of an ultraviolet absorber and glycidol, or an alkylene oxide in addition to the ultraviolet absorber, and its copolymer. It concerns application to cosmetics. Sunburn is usually an acute dermatitis that occurs when sunlight, especially ultraviolet rays, acts beyond the physiological tolerance of the skin, and its manifestations are known as erythema (sunburn) and darkening (suntan). . In general, the intensity of onset and subsequent course vary depending on the intensity and amount of ultraviolet rays that the skin receives, but first, it causes congestion of capillaries within the skin, followed by swelling, resulting in edema and erythema (sunburn) accompanied by water. occurs. After a few days, the inflammation subsides and the erythema disappears, and melanin pigment is deposited within the skin, causing it to darken (suntan).
transition to. Ultraviolet rays have a wavelength of 280 nm.
Short wavelength ultraviolet (UV-C) below, 280~320n
m medium wavelength ultraviolet region (UV-B) 320-400nm
Although it is classified as long-wavelength ultraviolet rays (UV-A), ultraviolet rays below 290nm are usually absorbed by the ozone layer, the atmosphere, etc. and do not reach the earth's surface, so 290-400nm
Ultraviolet rays (UV-B and UV-A) of 290 to 320 nm are biologically important, and of these, ultraviolet rays of 290 to 320 nm (UV-B) are mainly associated with acute erythematous effects (sunburn) and are associated with erythematous areas. called ultraviolet light,
Furthermore, ultraviolet rays (UV-A) in the range of 320 to 400 nm promote blackening (suntan) and are therefore called UV-A in the blackening region. Therefore, as a UV absorber, the minimum
It is essential to have a filter effect for ultraviolet light from 290 to 320 nm, and if necessary, from 320 nm to
It is also required to absorb 400nm ultraviolet light. As is well known, bunzophenone compounds, p-aminobenzoic acid compounds, and p-aminoacetophenone compounds have excellent ultraviolet absorption ability, from 280 nm onwards.
It has an absorption maximum over 350 nm, and by taking advantage of this property, it can be used with various derivatives as a photostabilizer for plastics, textiles, etc., and in the cosmetics field to prevent skin irritation and sunburn caused by sunlight, pigments, fragrances, etc. It has been used for the purpose of photostabilizing components. However, these substances themselves and many derivatives derived from them are originally fat-soluble, and derivatization is often aimed at increasing fat-solubility, which is an important factor in their use in cosmetics. Some of the water-soluble derivatives are ethylene oxide adducts to p-aminoacetophenone or 2
-Hydroxy-4-methoxybenzophenone-5
- Except for anionic derivatives typified by sulfonates (commonly known as sulisobenzone), they were all the same. Moreover, even these water-soluble derivatives have safety problems due to a decrease in absorbance due to an increase in molecular weight and effects on the skin, and cannot be said to be sufficient. In view of this current situation, the present inventors have discovered that water solubility can be achieved by introducing glyceryl groups into various UV absorbers by adding glycidol, etc., and have already proposed this as a standard UV absorber (specifically 1988-109454 and JP-A-58-110535). However, even in the above method, water solubility can be achieved only when 2 moles or more are added, and 1 mole is unavoidable in synthesis.
In view of the presence of molar adduct by-products (water-insoluble), something more efficient or more economical was desired. Therefore, the present inventors conducted research to obtain even better ultraviolet absorbers, and found that these ultraviolet absorbers, glycidol, and alkylene oxide were added as necessary to copolymerize two to three components. We have completed the present invention by discovering that safety can be improved by increasing the molecular weight, that absorbance can be controlled, and that the solubility itself can be varied from water-soluble to ethanol-soluble. The present invention is based on the general formula () X _l −Y _n −Z _o () [wherein, X is

[expression] or

[Formula] Y is one or more of CH ₂ CH ₂ O, CH ₂ CH (CH ₃ ) O, CH ₂ CH (C ₂ H ₅ ) O, CH ₂ CH ₂ CH ₂ CH ₂ O a mixture of , Z is then or: (However, R ₁ and R ₂ represent hydrogen or hydroxyl group); (However, A is carboxyl group: -COOH, alkoxycarbonyl group: -COOCH ₃ , -
COOC ₂ H ₅ , -COOC ₃ H ₇ , acetyl group: -
COCH ₃ ) In addition, l, m, and n each represent the number of moles added, and are 3≦l≦200, O≦m≦200, and 2≦n≦200. The present invention relates to a high molecular weight ultraviolet absorber represented by the following formula, and further relates to a cosmetic containing one or more of the above high molecular weight ultraviolet absorbers. Regarding the raw material components forming the high molecular weight ultraviolet absorber of the present invention, firstly, glycidol is mentioned as the X component, which makes it water-soluble. Next, as the Y component, one or more types of alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and tetramethylene oxide (THF) are selected and used. Here, alkylene oxide is used for two purposes. 1
One is the solubility control function from water solubility to ethanol solubility, and this is due to the number of carbon atoms,
It is closely related to the presence or absence of branches. Another feature is the molecular weight control function. When polymerization is carried out without using alkylene oxide, the degree of polymerization reaches a plateau at an average molecular weight of approximately 1,000 to 3,000, although there is some variation depending on the type of UV absorber. By using these together, the degree of polymerization is dramatically accelerated. Further, as the Z component, 2,4-dihydroxybenzophenone, 2,2',
4-trihydroxybenzophenone, 2,2',
Benzophenone compounds such as 4,4'-tetrahydroxybenzophenone, p-aminobenzoic acid and its esters (methyl, ethyl, propyl), p-aminobenzoic acid and its esters (methyl, ethyl, propyl),
Although various ultraviolet absorbers such as -aminoacetophenone can be mentioned, it is very difficult to use this substance directly as a polymerization component. In practical terms,
Considering the absorption maximum wavelength and the influence on solubility, p-
For aminobenzoic acid and p-aminoacetophenone systems, an amino group is introduced, and for benzophenone systems, a hydroxyl group at the 4-position, a heglycidyl imino group or a glycidyl ether group, is introduced and used for polymerization as a synthetic intermediate component. Although it is possible to polymerize the synthetic intermediate alone by thermal polymerization or other appropriate polymerization methods, the resulting polymer generally becomes a resin and becomes insoluble and infusible. In the present invention, the desired high-molecular-weight ultraviolet absorber is obtained by random addition polymerization of the above-mentioned X, Z2 components, and further the Y component as necessary. number l,
m and n are 3≦l≦200, 0≦m≦200, 2 considering the balance of solubility, ultraviolet absorption ability, and safety.
The range is ≦n≦200, and the average molecular weight is
It is preferably in the range of 1000 to 20000. Here, the characteristic point of the present invention is that by changing the type and composition ratio of the glyceryl group moiety and the alkyl ether group moiety in the above composition range, the solubility of the obtained polymer can be changed from water solubility to ethanol. In some cases, various changes can be made up to the level of solubility. For example, when ethylene oxide or propylene oxide is used as the alkylene oxide, it is water-soluble in a wide range of composition ratios, whereas when 1,2-butylene oxide or tetramethylene oxide (THF) is used, it is water-soluble. The composition ratio of glyceryl groups and alkyl ether groups in the polymer, when the alkyl ether group/glyceryl group is 1 or less, it is water soluble, when it is 2 or more, it is ethanol soluble, and when it is in the range of 1 to 2, it is the type of ultraviolet absorber. They tend to be water-soluble or ethanol-soluble. Since it is possible to arbitrarily change the solubility in this way, it becomes possible to provide a desired high molecular weight ultraviolet absorber depending on the form of the product in which it is used. The high molecular weight ultraviolet absorber of the present invention is a pale yellow transparent highly viscous liquid substance, for example, in the case of a benzophenone polymer, and has a wavelength range of 280 to 290 nm (UV-B).
It has an absorption maximum in the 320 nm to 330 nm (UV-A) region, and p-aminobenzoic acid-based polymers and p-aminoacetophenone-based polymers are transparent, pale yellow to reddish brown, highly viscous substances, and have a wavelength of 310 nm. Near (p-
(aminobenzoic acid type) and around 340 nm (p-aminoacetophenone type). This property indicates that p-aminobenzoic acid-based polymers have an effective filtering effect against ultraviolet rays in the erythema region, and p-aminoacetophenone-based polymers have an effective filter effect against ultraviolet rays in the blackening region. Furthermore, benzophenone polymers have been shown to be effective for both, making them extremely useful for sunscreen applications. These various polymers are blended in the form of lotions, emulsions, creams, white powders, foundations, ointments, etc., and can be particularly advantageously used in water-based products, for photostabilizing pigments, fragrances, etc., and for sunscreens. It is used for etc. In addition, the blending concentration at this time is approximately 0.01 to 30% based on the base, but depending on the type of base,
It is practical to select the optimum concentration depending on whether or not it is used in combination with other ultraviolet absorbers/cutting agents, the purpose of use, etc. The high molecular weight ultraviolet absorber polymer according to the present invention is
First, as a first step, glycidylimine or glycidyl ether (synthetic intermediate) is synthesized by adding epichlorohydrin to various ultraviolet absorbers and then by alkaline saponification. Furthermore, in the second step, polymerization is carried out using two or three components of glycidol, a synthetic intermediate, and optionally alkylene oxide in the presence of a catalyst. Examples of synthesis of the polymer of the present invention are shown below. Synthesis example 1 2,4-dihydroxybenzophenone polymer (EtOH soluble) 1-3 equipped with a stirrer, cooler, and thermometer
214 g (1 mol) of 2,4-dihydroxybenzophenone and 370 g of epichlorohydrin in a neck flask.
(4 mol) was added. The mixture was heated to 100° C. in an oil bath with stirring, and granular sodium hydroxide was added in 6 portions over 2 hours. Thereafter, stirring was continued for 2 hours at the same temperature, and after cooling, the precipitated common salt was filtered out. After concentrating the filtrate, it was crystallized from ethanol to obtain 2-hydroxybenzophenone-4-glycidyl ether.
Obtained as pale yellow needle crystals with mp 103-104°C. 5.4 g (0.02 mol) of the obtained crystals were placed in a 300 ml three-necked flask, dissolved in 100 ml of tetrahydrofuran, and 0.1 ml of boron trifluoride ethyl ether complex was added. A solution of 14.8 g of glycidol diluted with 50 ml of tetrahydrofuran was added dropwise to this over 1 hour, and the mixture was allowed to react at room temperature for another 1 hour. Unreacted tetrahydrofuran was distilled off to obtain a polymer as a pale yellow viscous liquid. Optical properties and average molecular weight of Γ polymer Ultraviolet absorption λmax (EtOH) 290nm, 324nm
(See Figure 1) Infrared absorption 3370cm ^-1 CH stretching vibration 2940cm ^-1 and 2880cm ^-1
CH 〃 1625cm ^-1 C=O 〃 1260cm ^-1
= C-O-C antisymmetric stretching 1100cm ^-1 C-O stretching vibration 700cm ^-1 Molecular weight measurement by benzene nucleus out-of-plane deformation GPC (in terms of pullulan) _o =
9000 Synthesis Example 2 2,4-dihydroxybenzophenone polymer (water soluble) 200 equipped with a stirrer, cooler, and dropping funnel
ml of 3-necked flask, add 2 as shown in Synthesis Example 1.
-Hydroxybenzophenone-4-glycidyl ether 5.4g (0.02mol) and dioxane 20ml were added and dissolved, boron trifluoride ethyl ether complex 0.4
ml was added and the temperature was set at 70°C. This includes glycidol 14.8
g was added dropwise over 30 minutes, and the reaction was then carried out at 70°C for 1 hour. Dioxane was distilled off to obtain a polymer as a pale yellow viscous liquid. Optical properties and average molecular weight of Γ polymer Ultraviolet absorption λmax (MeOH) 290nm. 324nm
(See Figure 2) Infrared absorption 3370cm ^-1 O-H stretching vibration 2940cm ^-1 and 2880cm ^-1 C-H stretching vibration 1625cm -1 C=O stretching vibration 1260cm ^{-1 =} C-O-C antisymmetrical stretching 1100cm ^-1 C-O stretching vibration 700cm ^-1 Benzene nucleus out-of-plane bending Molecular weight measurement by GPC (in terms of pullulan) _o = 2000 Synthesis example 3 Ethyl PABA polymer (water soluble) A stirrer, cooler, and dropping funnel were attached. 1
82.5g of ethyl PABA in a 3-necked flask
(0.5 mol) was added and dissolved in 400 ml of dichloromethane, and further 5 ml of boron trifluoride ethyl ether complex was added. While stirring, 47 g (0.5 mol) of epichlorohydrin was added dropwise at 40° C. or lower over 1 hour. Thereafter, it was stirred at 50°C for 12 hours, dichloromethane was distilled off, and then crystallized from chloroform.
N-(2-hydroxy-3-chloropropyl)-
Ethyl PABA was obtained as white crystals with mp 103-104 °C. Next, 8.9 g (0.12 mol) of calcium hydroxide was placed in a 500 ml beaker, and 300 ml of water was added to disperse it. 15.5g of crystals obtained from this
(0.06 mol) dissolved in 50 ml of tetrahydrofuran was poured into the mixture and stirred at room temperature for 20 hours. Then, remove excess calcium hydroxide,
The filtrate was extracted with ethyl acetate, the ethyl acetate layer was concentrated, and then crystallized from ether.
Ethyl aminobenzoate was obtained as white crystals with mp 69-70°C. Next, 50 ml of chloroform was placed in a 300 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel, and 0.5 ml of boron trifluoride ethyl ether complex was added. To this, 6.7 g (0.03 mol) of ethyl glycidyl-p-aminobenzoate,
A solution of 13.4 g (0.18 mol) of glycidol in 100 ml of chloroform was added dropwise under reflux conditions for 3 hours. After the dropwise addition, the mixture was further stirred for 1 hour, the chloroform layer was decanted, and the resulting precipitate (polymerized product) was taken out. The polymer was a reddish brown water-soluble viscous liquid. Optical properties and average molecular weight of Γ polymer Ultraviolet absorption λmax (MeOH) 309 nm (see Figure 3) Infrared absorption 3400 cm ^-1 O-H stretching vibration 2950 cm ^-1 and 2900 cm ^-1
C-H stretching vibration 1680cm ^-1 C=O stretching vibration 1290cm ^-1 Carom-N stretching vibration 1100cm ^-1 C-O stretching vibration 835cm ^-1 Benzene nucleus out-of-plane bending vibration Molecular weight measurement by GPC (in terms of pullulan) _o = 3000 Synthesis Example 4 p-aminoacetophenone polymer (water soluble) 1 equipped with a stirrer, cooler, and dropping funnel
p-aminoacetophenone in a 3-necked flask
67.5g (0.5mol), zinc perchlorate hexahydrate
Add 1.34g (0.005mol) and 400ml of dioxane.
was added and dissolved. At below 50℃ while stirring,
47 g (0.5 mol) of epichlorohydrin was added dropwise over 1 hour. After that, it was stirred at 60℃ for 48 hours, dioxane was distilled off, and then fractionated with a silica gel column to obtain N-(2-hydroxy-4-chloropropyl)-p-aminoacetophenone with mp79-82.
Obtained as white crystals at ℃. Next, add 8.9g (0.12mol) of calcium hydroxide to a 500ml beaker.
300 ml of water was added to disperse. 13.7 g (0.06 mol) of the crystals obtained were added to tetrahydrofuran.
The solution was poured into 50 ml and stirred at room temperature for 20 hours. After that, excess calcium hydroxide was filtered off, the filtrate was extracted with ethyl acetate, the ethyl acetate layer was concentrated, and then crystallized from ether to obtain glycidyl-p-aminoacetophenone, mp92-93℃.
Obtained as white crystals. Stirrer, cooler,
20 ml of propylene oxide was placed in a 300 ml three-necked flask equipped with a dropping funnel, and 0.05 ml of boron trifluoride ethyl ether complex was added. Add to this 12 g (0.05 mol) of glycidyl-p-aminoacetophenone and 37 g of glycidol.
(0.5 mol) dissolved in 20 ml of propylene oxide was added dropwise over 1 hour, and the reaction was further allowed to proceed at room temperature for 1 hour. Unreacted propylene oxide was distilled off to obtain a polymer as a pale yellow viscous liquid. Optical properties and average molecular weight of Γ polymer Ultraviolet absorption λmax (MeOH) 337 nm (4th
(See figure) Infrared absorption 3400cm ^-1 O-H stretching vibration 2950cm ^-1 and 2900cm ^-1 C-H stretching vibration 1645cm ^-1 C=O stretching vibration 1290cm ^-1 Carom-N stretching vibration 1100cm ^-1 C-O stretching vibration 820cm ^-1 Benzene nucleus out-of-plane bending Molecular weight measurement by GPC (in terms of pullulan) _o = 15000 Next, in order to confirm the safety of the high molecular weight UV absorber of the present invention, an animal test (6 Angora rabbits) was conducted. The results are shown in Table-1. The test method is as follows. Γ Skin primary irritation test: A sample (concentration
100%, 30%, 10%) were administered transdermally and observed the next day. Note that ethanol was used as the dilution solvent.

〔material〕

X component: glycidol Y component: tetramethylene oxide (THF) Z component: 2-hydroxybenzophenone-4-glycidyl ether (synthetic intermediate)

[Table] As shown in Table 2, the solubility of the high molecular weight UV absorber of the present invention varies depending on the ratio of the glyceryl group part to the alkyl ether group part. For example, when an ethanol-soluble polymer is blended, It can be applied to various formulation systems, such as making it possible to create water-resistant cosmetics that form a water-insoluble film after ethanol evaporates on the skin. Next, a formulation example of the high molecular weight ultraviolet absorber of the present invention will be shown. The blending ratio is in parts by weight. Example 1 Suntan lotion ethanol 8.0 Propylene glycol 5.0 Hyalulamine 0.1 Polyoxyethylene (50) hydrogenated castor oil 0.5 Citric acid 0.02 Sodium citrate 0.1 Methylparaben 0.05 Fragrance 0.23 Water 83.0 Ethyl PABA-based high molecular weight ultraviolet light Absorbent (Synthesis Example 3) 3.0 Example 2 Sunscreen Cream Stearic Acid 4.5 Spell Wax 3.5 Setanol 2.5 Lanolin 1.5 Isopropyl myristate 6.0 Squalane 4.5 Polyoxyethylene sorbitan monostearate
4.5 Sorbitan monostearate 1.0 Propylene glycol 3.5 Butylparaben 0.2 Butylated hydroxytoluene 0.05 Fragrance 0.25 Water 50.0 Ethyl PABA-based high molecular weight UV absorber (Synthesis example 3) 3.0 p-Aminoacetophenone-based high molecular weight UV absorber (Synthesis example 4) 5.0 2,4-dihydroxybenzophenone-based high molecular weight UV absorber (Synthesis Example 2) 10.0 Example 3 Water-resistant sunscreen lotion ethanol 77.0 Polyoxyethylene (50) hydrogenated castor oil 0.5 Olive oil 0.1 Glycerin 0.5 Sodium liponucleic acid 0.1 Cationized cellulose 0.1 Fragrance 0.2 2,4-dihydroxybenzophenone-based high molecular weight ultraviolet absorber (Synthesis Example 1) 10.0 Water 11.5

[Brief explanation of drawings]

Figure 1 shows the ultraviolet absorption spectrum (EtOH) of the 2,4-dihydroxybenzophenone-based high molecular weight ultraviolet absorber (ethanol-soluble) produced in Synthesis Example 1. Figure 2 shows the 2,4-
Ultraviolet absorption spectrum (MeOH) of dihydroxybenzophenone-based high molecular weight UV absorber (water soluble). Figure 3 shows ethyl produced in Synthesis Example 3.
Ultraviolet absorption spectrum (MeOH) of PABA-based high molecular weight UV absorber (water soluble). Figure 4 shows the ultraviolet absorption spectrum (MeOH) of the p-aminoacetophenone-based high molecular weight ultraviolet absorber (water soluble) produced in Synthesis Example 4.

Claims (1)

[Claims] 1. A high molecular weight ultraviolet absorber represented by the general formula (). X _l −Y _n −Z _o () [where X is [formula] or [formula] Y is CH ₂ CH ₂ O, CH ₂ CH (CH ₃ ) O, CH ₂ CH (C ₂ H ₅ ) O , CH ₂ CH ₂ CH ₂ CH ₂ O, or a mixture of two or more of them; Z is the following or; (However, R ₁ and R ₂ represent hydrogen or hydroxyl group); (However, A is carboxyl group: -COOH, alkoxycarbonyl group: -COOCH ₃ , -
COOC ₂ H ₅ , -COOC ₃ H ₇ , acetyl group: -
COCH ₃ ) In addition, l, m, and n each represent the number of moles added, and are 3≦l≦200, O≦m≦200, and 2≦n≦200. ] 2. A cosmetic containing one or more types of high molecular weight ultraviolet absorbers represented by the general formula (). X _l −Y _n −Z _o () [where X is [formula] or [formula] Y is CH ₂ CH ₂ O, CH ₂ CH (CH ₃ ) O, CH ₂ CH (C ₂ H ₅ ) O , CH ₂ CH ₂ CH ₂ CH ₂ O, or a mixture of two or more of them, Z is the following or: (However, R ₁ and R ₂ represent hydrogen or hydroxyl group); (However, A is carboxyl group: -COOH, alkoxycarbonyl group: -COOCH ₃ , -
COOC ₂ H ₅ , -COOC ₃ H ₇ , acetyl group: -
COCH ₃ ) In addition, l, m, and n each represent the number of moles added, and are 3≦l≦200, O≦m≦200, and 2≦n≦200. ]